US20190032231A1 - Metal-containing cluster catalyst, and electrode for carbon dioxide reduction and carbon dioxide reduction apparatus including the same - Google Patents

Metal-containing cluster catalyst, and electrode for carbon dioxide reduction and carbon dioxide reduction apparatus including the same Download PDF

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US20190032231A1
US20190032231A1 US16/144,800 US201816144800A US2019032231A1 US 20190032231 A1 US20190032231 A1 US 20190032231A1 US 201816144800 A US201816144800 A US 201816144800A US 2019032231 A1 US2019032231 A1 US 2019032231A1
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metal
carbon dioxide
cluster
electrode
copper
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Yoshinori KAZAMA
Hideki Aizawa
Toshio Tani
Kojiro Inamori
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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    • C25B11/0478—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/04—Methane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/06—Ethane
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B3/04—
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B9/10—
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present disclosure relates to a metal-containing cluster catalyst, and also to an electrode for carbon dioxide reduction and a carbon dioxide reduction apparatus including the same.
  • a catalyst means a substance that changes the reaction rate of a substance system causing a chemical reaction but itself is not chemically changed, and selectivity and reaction efficiency with respect to a specific chemical reaction differ depending on the kind (material, morphology or the like) of the catalyst.
  • Metal materials are widely used as catalyst materials, and noble metal materials are particularly of importance due to their good reactivity.
  • Japanese Patent Application Laid-Open No. 2007-090164 discloses a noble metal catalyst having selectivity in a specific reaction.
  • attention is also being focused on oxide catalysts.
  • Japanese Patent Application Laid-Open No. 2007-301470 discloses an oxide catalyst having excellent catalytic activity and selectivity.
  • the present disclosure is related to providing a metal-containing cluster catalyst capable of accelerating/controlling the reduction reaction of carbon dioxide with high catalytic activity and selectivity, and an electrode for carbon dioxide reduction and a carbon dioxide reduction apparatus including the same.
  • a metal-containing cluster catalyst includes a cluster including at least one metal atom (M), a metal of each of the at least one metal atom (M) being selected from the group consisting of gold, silver, copper, platinum, rhodium, palladium, nickel, cobalt, iron, manganese, chromium, iridium, and ruthenium, wherein the metal-containing cluster catalyst is used for reducing carbon dioxide.
  • an electrode for carbon dioxide reduction includes a metal-containing cluster catalyst, the metal-containing cluster catalyst including a cluster including at least one metal atom (M), a metal of each of the at least one metal atom (M) being selected from the group consisting of gold, silver, copper, platinum, rhodium, palladium, nickel, cobalt, iron, manganese, chromium, iridium, and ruthenium, wherein the metal-containing cluster catalyst is used for reducing carbon dioxide.
  • M metal of each of the at least one metal atom (M) being selected from the group consisting of gold, silver, copper, platinum, rhodium, palladium, nickel, cobalt, iron, manganese, chromium, iridium, and ruthenium
  • a carbon dioxide reduction apparatus includes an electrode for carbon dioxide reduction, the electrode for carbon dioxide reduction including a metal-containing cluster catalyst including a cluster including at least one metal atom (M), a metal of each of the at least one metal atom (M) being selected from the group consisting of gold, silver, copper, platinum, rhodium, palladium, nickel, cobalt, iron, manganese, chromium, iridium, and ruthenium, wherein the metal-containing cluster catalyst is used for reducing carbon dioxide.
  • a metal-containing cluster catalyst including a cluster including at least one metal atom (M), a metal of each of the at least one metal atom (M) being selected from the group consisting of gold, silver, copper, platinum, rhodium, palladium, nickel, cobalt, iron, manganese, chromium, iridium, and ruthenium, wherein the metal-containing cluster catalyst is used for reducing carbon dioxide.
  • the metal-containing cluster catalyst of the present disclosure exhibits excellent performance in the reduction reaction of carbon dioxide.
  • FIG. 1 is a block diagram showing the configuration of an electrolysis apparatus 1 .
  • FIG. 2A is a schematic diagram showing the configuration of an electrolysis cell 3 .
  • FIG. 2B is a diagram showing the configuration of an electrolysis cell 3 a.
  • FIG. 3 is a general schematic diagram showing an electrode producing apparatus 27 used in producing an electrode including a copper porous body according to Comparative Examples of the present disclosure.
  • FIG. 4 is a schematic diagram showing a reduction testing apparatus 50 when a reduction test is performed on Examples.
  • FIG. 5 is an enlarged schematic diagram showing an electrolysis cell 53 portion (H portion) of the reduction testing apparatus 50 of FIG. 4 .
  • the metal-containing cluster catalyst according to the present embodiment is a cluster including at least one metal atom (M), a metal of each of the least one metal atom (M) being selected from the group consisting of gold (Au), silver (Ag), copper (Cu), platinum (Pt), rhodium (Rh), palladium (Pd), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), chromium (Cr), iridium (Ir), and ruthenium (Ru).
  • the term “cluster” refers to an atomic aggregate wherein a plurality of atoms are bonded.
  • Such metal-containing cluster catalyst exhibits excellent performance in reduction reaction of carbon dioxide, and thus is suitably used as a catalyst for reducing carbon dioxide.
  • the metal atom (M) contained in the cluster according to the present embodiment is of a metal selected from Au, Ag, Cu, Pt, Rh, Pd, Ni, Co, Fe, Mn, Cr, Ir, and Ru.
  • the cluster (hereinafter, referred to as “metal-containing cluster”) exhibits excellent performance in the reduction reaction of carbon dioxide.
  • the metal atom (M) is preferably of a metal selected from Cu, Ag, Pd, and Au.
  • the metal atom (M) is more preferably of Cu.
  • the metal-containing cluster is not particularly limited as long as the metal-containing cluster contains the metal atoms (M) described above.
  • the metal-containing cluster may be a cluster composed of a simple substance of the metal atom (M), an alloy containing the metal atom (M), a metal oxide containing the metal atom (M), or a composite oxide containing the metal atom (M).
  • the alloy or composite oxide containing the metal atom (M) may be an alloy or composite oxide containing at least one metal atom, a metal of each of the at least one metal being selected from the group consisting of Au, Ag, Cu, Pt, Rh, Pd, Ni, Co, Fe, Mn, Cr, Ir, and Ru.
  • the alloy or composite oxide containing the metal atom (M) may be an alloy or composite oxide containing metal atoms of two or more metals selected from the above, or an alloy or composite oxide containing a metal atom other than the above capable of forming an alloy or a composite with the metal atom (M).
  • the metal-containing cluster is preferably composed of a metal oxide containing the metal atom (M).
  • the metal-containing cluster is preferably composed of a simple substance of the metal atom (M) or a metal oxide of the metal atom (M) and represented by the following general formula (1):
  • M represents the aforementioned metal atom (M)
  • O represents an oxygen atom
  • n and m are integers.
  • n is preferably 30 or less, and more preferably 15 or less. n is preferably 6 or more, and more preferably 9 or more. With the aforementioned range, the size of the cluster can be controlled, and a degree of oxidation (valence) can also be controlled.
  • m is, with respect to n, such that a ratio m/n is preferably 0 to 2, more preferably 0.5 to 1.5, and still more preferably 0.55 to 0.75.
  • the aforementioned range provides a degree of oxidation specific to the cluster, and thus catalyst performance improves.
  • the metal-containing cluster is composed of a simple substance of the metal atom (M).
  • a primary particle diameter of the metal-containing cluster is preferably 0.1 to 3.0 nm, more preferably 0.5 to 2.0 nm, and still more preferably 0.6 to 1.2 nm.
  • the aforementioned range provides an increase in the total surface area of particles of the metal-containing cluster and a degree of oxidation specific to the cluster, and thus catalyst performance improves.
  • the primary particle diameter is measured using mass spectrometry (MS), a transmission electron microscope (TEM), a dynamic light scattering method (DLS) or the like.
  • the metal-containing cluster can be produced in a liquid phase or a gas phase by a known method.
  • a method for producing the metal-containing cluster in the liquid phase include a method using a dendrimer.
  • a method for producing the metal-containing cluster in the gas phase include an ion sputtering method, a plasma discharge method, and a laser vaporization method (laser ablation).
  • laser ablation laser ablation
  • Laser ablation is a phenomenon in which clusters scatter when a solid surface is irradiated with strong laser light and a surface layer that has locally come to an increased temperature evaporates.
  • the laser ablation may also be referred to as laser sputtering.
  • An apparatus performing laser ablation is not particularly limited, and laser ablation can be performed by using a known apparatus.
  • a metal cluster can be produced by, mixing a solution containing a dendrimer and a solution containing a metal compound corresponding to an intended metal-containing cluster to synthesize a metal complex of the dendrimer, and performing: (1) a method in which the metal complex is reduced by reduction using a reducing agent such as sodium borohydride, electrochemical reduction, photochemical reduction or the like, to deposit a metal on the dendrimer; (2) a method in which a solution containing the dendrimer metal complex is heated to remove a solvent, to thereby deposit a metal or a salt thereof on the dendrimer; or the like.
  • a reducing agent such as sodium borohydride, electrochemical reduction, photochemical reduction or the like
  • Examples of the dendrimer include a polyamideamine (PAMAM) dendrimer, a polypropyleneimine (PPI) dendrimer, and a phenylazomethine dendrimer (DPA).
  • Examples of the metal compound include a chloride and nitrate of the metal corresponding to the intended metal-containing cluster.
  • known solvents such as water and alcohol may be used as the solvent.
  • a carbon material encapsulating the metal-containing cluster is obtained by firing the metal-containing cluster obtained as described above.
  • the firing can be, in the case of a high temperature (for example, 400° C. or above), performed in an inactive gas atmosphere such as nitrogen or a rare gas including argon, and, in the case of a comparatively low temperature (for example, 200° C. or above), can be performed in the air.
  • a heat treatment can also be performed in a reduction atmosphere such as hydrogen.
  • the form of use of the metal-containing cluster catalyst according to the present embodiment is not particularly limited, and the metal-containing cluster catalyst is preferably used as a composite material with the metal-containing cluster catalyst supported on a carrier.
  • the carrier examples include, but are not particularly limited to, carbon, a metal, a semiconductor, ceramics, and a polymer.
  • the carrier may be appropriately selected depending on the application, use environment or the like of the composite material.
  • the carrier is preferably carbon or a metal.
  • the carrier is preferably a semiconductor.
  • the polymer suitably used as the carrier is, for example, a chainlike polymer, a single polymer or the like.
  • the chainlike polymer include polyvinyl pyrrolidone (PVP), polyethylene glycol (PEG), and polyvinylidene fluoride (PVdF).
  • the single polymer include ferritin, thiolate, phosphine, and alkine.
  • the metal-containing cluster catalyst according to the present embodiment can be suitably used as a material of the electrode for carbon dioxide reduction. Therefore, the electrode for carbon dioxide reduction according to the present embodiment preferably contains the above metal-containing cluster catalyst.
  • a method for forming the electrode is not particularly limited, and can be performed by a known method.
  • an electrode including the metal-containing cluster catalyst can be produced by dispersing the aforementioned carbon material encapsulating the metal-containing cluster using the dendrimer in a solvent to obtain a dispersion liquid, mixing the dispersion liquid with a binder to obtain a mixture, mixing the mixture with a conductive material if needed to obtain a coating material, and directly applying the coating material to a current collector, an ion-exchange membrane or the like, followed by drying.
  • binder examples include, but are not particularly limited to, polyvinylidene fluoride (PVdF), a mixture of carboxymethylcellulose sodium (CMC) and styrene butadiene copolymer (SBR), and polytetrafluoroethylene (PTFE).
  • PVdF polyvinylidene fluoride
  • CMC carboxymethylcellulose sodium
  • SBR styrene butadiene copolymer
  • PTFE polytetrafluoroethylene
  • the electrode including the metal-containing cluster catalyst according to the present disclosure can be suitably used as a cathode electrode of the carbon dioxide reduction apparatus to be described later.
  • the carbon dioxide reduction apparatus preferably include the aforementioned electrode for carbon dioxide reduction.
  • a method for producing the apparatus is not particularly limited, and can be performed by a known method.
  • the electrolysis apparatus 1 mainly includes an electrolysis cell 3 , a gas recovery apparatus 5 , an electrolysis solution circulation apparatus 7 , a carbon dioxide supply part 9 , and a power supply 11 .
  • the configuration of the carbon dioxide reduction apparatus according to the present embodiment is not limited to the configuration shown in FIG. 1 , and the carbon dioxide reduction apparatus may be appropriately modified and used if needed.
  • the electrolysis cell 3 is a portion that reduces the target substance, and in the present embodiment, particularly a portion that reduces carbon dioxide (also includes the case where it is a carbonate ion or carbonate in a solution. Hereinafter, merely referred to as carbon dioxide or the like).
  • the electrolysis cell 3 is supplied with electric power from the power supply 11 .
  • the electrolysis cell 3 will be described in detail later.
  • the electrolysis solution circulation apparatus 7 is a portion that circulates a cathode side electrolysis solution to the cathode electrode of the electrolysis cell 3 .
  • the carbon dioxide supply part 9 is a tank or the like that stores carbon dioxide, for example, and can hold carbon dioxide and supply a predetermined amount of carbon dioxide to the electrolysis solution circulation apparatus 7 .
  • the carbon dioxide supply part 9 can also hold a solution already in the form of a carbonate ion, carbonate or the like in place of the carbon dioxide, and supply a predetermined amount of the solution to the electrolysis solution circulation apparatus 7 .
  • the gas recovery apparatus 5 is a portion that recovers a gas generated by reduction by the electrolysis cell 3 .
  • the gas recovery apparatus 5 is capable of collecting a gas such as a hydrocarbon generated at the cathode electrode of the electrolysis cell 3 .
  • the gas recovery apparatus 5 may allow the gas to be separated into each type of gas.
  • the electrolysis apparatus functions as follows. As described above, an electrolysis potential from the power supply is applied to the electrolysis cell.
  • the electrolysis solution is supplied to the cathode electrode of the electrolysis cell by the electrolysis solution circulation apparatus. At the cathode electrode of the electrolysis cell, carbon dioxide or the like in the supplied electrolysis solution is reduced. When the carbon dioxide or the like is reduced, a hydrocarbon such as ethane or ethylene is mainly generated.
  • the hydrocarbon gas generated at the cathode electrode is recovered by the gas recovery apparatus.
  • the gas In the gas recovery apparatus, the gas can be separated and stored if needed.
  • the concentration of carbon dioxide or the like in the electrolysis solution decreases.
  • Carbon dioxide or the like decreased due to the reduction reaction is always refilled, and the concentration of carbon dioxide is always maintained in a predetermined range.
  • a part of the electrolysis solution is recovered by the electrolysis solution circulation apparatus, and an electrolysis solution having a predetermined concentration is always supplied.
  • the hydrocarbon can be always generated under a given condition at the electrolysis cell 3 .
  • FIG. 2A is a diagram showing an example of the configuration of the electrolysis cell 3 .
  • the electrolysis cell 3 mainly includes a tank 16 a as a cathode tank, a metal mesh 17 , a cathode electrode 19 , an ion-exchange membrane 21 , an electrolyte 23 , an anode electrode 25 , and a tank 16 b as an anode tank.
  • the configuration of an electric cell of the carbon dioxide reduction apparatus according to the present embodiment is not limited to the configuration shown in FIG. 2A , and the configuration of the electrolysis cell may be appropriately modified and used if needed.
  • Electrolysis solutions 15 a and 15 b are respectively held in the cathode tank 16 a and the anode tank 16 b .
  • a hole for recovering a generated gas is formed in the upper part of the tank 16 a on the side of the cathode electrode, and is connected to the gas recovery apparatus, not shown. That is, the gas generated at the cathode electrode is recovered from the hole.
  • a pipe or the like is connected to the cathode tank 16 a , and is connected to the electrolysis solution circulation apparatus 7 , not shown. That is, the electrolysis solution 15 a in the cathode tank 16 a can be always circulated by the electrolysis solution circulation apparatus 7 .
  • the circulation of the electrolysis solution on the side of the anode tank 16 b may also be similarly allowed if needed.
  • the electrolysis solution 15 a as a cathode electrolysis solution is preferably an electrolysis solution capable of dissolving a large amount of carbon dioxide or the like.
  • an alkaline solution such as a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, monomethanolamine, methylamine, other liquid amine, or a mixed solution of the liquid amine and electrolyte aqueous solution, or the like is used.
  • Acetonitrile, benzonitrile, methylene chloride, tetrahydrofuran, propylene carbonate, dimethylformamide, dimethyl sulfoxide, methanol, ethanol or the like may be used.
  • the electrolyte aqueous solution is not particularly limited, and a potassium chloride aqueous solution, a sodium chloride aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sodium hydrogen carbonate aqueous solution, a potassium carbonate aqueous solution or the like may be used, for example.
  • the electrolysis solution 15 b as an anode electrolysis solution is not particularly limited, and a potassium chloride aqueous solution, a sodium chloride aqueous solution, a sodium hydrogen carbonate aqueous solution, a potassium hydrogen carbonate aqueous solution or the like may be used, for example.
  • the metal mesh 17 is a member connected to the anode electrode side of the power supply and applies an electric current to the cathode electrode 19 .
  • the metal mesh 17 is, for example, a copper mesh or a stainless steel mesh, and for example, a stainless steel SUS304 400 mesh (25 ⁇ m in thickness, manufactured by Nilaco Corporation) may be used.
  • the ion-exchange membrane 21 is not particularly limited, and, for example, a hydrocarbon-based, perfluorocarbon-based ion-exchange membranes or the like may be used.
  • the ion-exchange membrane 21 is particularly desirably a negative ion exchange membrane, and a Nafion membrane, a polyvinylidene fluoride (PVDF) membrane or the like may be used.
  • PVDF polyvinylidene fluoride
  • SELEMION (registered trademark) AMV” manufactured by Asahi Glass Co., Ltd. may be used.
  • the ion-exchange membrane 21 is used when manufacturing the cathode electrode 19 to be described later, and exhibits a function as the support member of the metal-containing cluster catalyst constituting the cathode electrode 19 .
  • the use of the ion-exchange membrane as a support member provides a simple configuration of a reduction part during electrolysis described later.
  • the electrolyte 23 is provided if needed.
  • the electrolyte 23 interposed between the ion-exchange membrane 21 and the anode electrode 25 to be described later is not particularly limited, and a polymer electrolyte such as polyvinylidene fluoride, polyacrylic acid, polyethylene oxide, polyacrylonitrile, or polymethyl methacrylate, or a potassium chloride aqueous solution, a sodium chloride aqueous solution or the like may be used.
  • the anode electrode 25 is connected to a positive electrode of the power supply.
  • the anode electrode 25 is not particularly limited, and, for example, titanium, platinum, titanium coated with platinum (Ti/Pt), stainless steel, copper, carbon or the like may be used. Ti/Pt is particularly preferable since deterioration is less.
  • the shape to be used is not particularly limited, and may be a plate shape, a punching metal shape, a mesh shape, or a nonwoven fabric shape. In terms of reducing the thickness of the electrolysis cell, and allowing the use even if the electrolysis cell has a curved shape, the nonwoven fabric shape is preferable.
  • An electrode including the metal-containing cluster catalyst according to the present disclosure is used as the cathode electrode 19 .
  • the use of the electrode including the metal-containing cluster catalyst according to the present disclosure as the cathode electrode 19 makes it possible to increase the amount of carbon dioxide reduced and to selectively control the reduction reaction of the carbon dioxide. Reduction efficiency can also be improved in respect of selectivity.
  • an electrolysis cell 3 a as shown in FIG. 2B may also be used.
  • the electrolysis cell 3 a has a configuration substantially similar to that of the electrolysis cell 3 , but contrary to the electrolysis cell 3 in which elements each having a plate shape are stacked, each elements are sequentially arranged substantially concentrically from the center to the outer periphery in a radial direction. Since each of the elements constituting the electrolysis cell 3 a is similar to each of the elements constituting the electrolysis cell 3 , like description will be omitted.
  • a chloroform solution of a phenylazomethine dendrimer and an acetone solution of copper chloride of 12 molar equivalents with respect to the dendrimer were mixed to synthesize a phenylazomethine dendrimer copper complex.
  • an excessive amount of sodium borohydride was added to reduce the phenylazomethine dendrimer copper complex, and a phenylazomethine dendrimer copper cluster was synthesized.
  • the synthesized phenylazomethine dendrimer copper cluster was fired in a nitrogen atmosphere to synthesize a carbon material encapsulating a copper-containing cluster.
  • the obtained carbon material enxapsulating a copper-containing cluster was dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a dispersion liquid, and polyvinylidene fluoride (PVDF) as a binder was added to the dispersion liquid, followed by mixing to obtain a coating material.
  • the coating material was applied onto an ion-exchange membrane, followed by drying, to produce an electrode including a copper-containing cluster catalyst.
  • Example 2 a carbon material encapsulating a copper-containing cluster, and an electrode including a copper-containing cluster catalyst including such carbon material were produced by a method similar to that of Example 1 except that the firing atmosphere of a phenylazomethine dendrimer copper cluster was air atmosphere in place of the nitrogen atmosphere, and the firing temperature was lower than that of Example 1.
  • Example 3 a carbon material encapsulating a copper-containing cluster, and an electrode including a copper-containing cluster catalyst including such carbon material were produced by a method similar to that of Example 1 except that the firing temperature of a phenylazomethine dendrimer copper cluster was lower than that in Example 1.
  • Example 4 a carbon material encapsulating a copper-containing cluster, and an electrode including a copper-containing cluster catalyst including such carbon material were produced by a method similar to that of Example 1 except that a phenylazomethine dendrimer copper cluster was fired in a nitrogen atmosphere, and then further fired in a hydrogen atmosphere.
  • Example 5 a carbon material encapsulating a silver-containing cluster, and an electrode including a silver-containing cluster catalyst including such carbon material were produced by a method similar to that of Example 1 except that a phenylazomethine dendrimer silver complex was synthesized by mixing a chloroform solution of a phenylazomethine dendrimer with an acetone solution of silver nitrate of 12 molar equivalents with respect to the dendrimer.
  • Comparative Example 1 With a method to be shown later, copper was deposited on an ion-exchange membrane by an electroless plating method to obtain an electrode having a copper porous body in which the deposited copper particles are aggregated.
  • Comparative Example 2 an electrode having a copper porous body was obtained by a method similar to that of Comparative Example 1 except that the electrode produced in Comparative Example 1 was fired in an air atmosphere.
  • Comparative Example 3 an electrode having a copper porous body was obtained by a method similar to that of Comparative Example 1 except that the electrode produced in Comparative Example 1 was fired in a nitrogen atmosphere.
  • Comparative Example 4 a method similar to that of Comparative Example 1 was performed except that 30 mL of a copper acetate aqueous solution of 5 mmol/L of Comparative Example 1 was changed to 30 mL of a silver nitrate aqueous solution of 5 mmol/L, and an electrode having a silver porous body was produced.
  • composition analysis and valence evaluation were performed for the above metal-containing cluster and metal-containing porous body constituting the catalyst using an inductively-coupled plasma sample analysis method and X-ray photoemission spectroscopy.
  • Example 5 As a sample for the analysis, in each of Examples 1 to 4, a carbon material containing a copper-containing cluster before producing the electrode was used, and in Example 5, the carbon material containing a silver-containing cluster before producing the electrode was used. In each of Comparative Examples 1 to 4, a metal material obtained by scraping and separating the porous body part on the ion-exchange membrane was used.
  • FIG. 5 is a diagram showing an electrolysis cell 53 , and is an enlarged view of an H portion in FIG. 4 .
  • the reduction testing apparatus 50 mainly includes a first tank 51 a , a second tank 51 b , an electrolysis cell 53 , a power supply 55 , an analysis tube 59 , and a supply tube 61 .
  • the two tanks 51 a and 51 b are divided by the electrolysis cell 53 .
  • Sodium hydrogen carbonate solution 57 is placed in each of the first tank 51 a and the second tank 51 b .
  • a sodium hydrogen carbonate solution of 50 mmol/L was used as the sodium hydrogen carbonate solution 57 , and 30 mL of a solution was used for each tank.
  • the upper part of the first tank 51 a is sealed with a lid.
  • the supply tube 61 and the analysis tube 59 are provided so as to pass through the lid.
  • the supply tube 61 is connected to a carbon dioxide supply source, not shown, and an end portion of the supply tube 61 is immersed in the sodium hydrogen carbonate solution 57 .
  • the end portion of the supply tube 61 extends to the vicinity of the lower base part of the first tank 51 a .
  • the sodium hydrogen carbonate solution 57 in the first tank 51 a is always agitated by supplying carbon dioxide from the supply tube 61 so that the concentration of the sodium hydrogen carbonate solution 57 is substantially maintained at a given value. Therefore, the same effect as that of the circulation of the sodium hydrogen carbonate solution 57 in the first tank 51 a can be obtained.
  • the end portion of the analysis tube 59 passes through the lid part, and is arranged in a gas part between the lid part and the surface of the solution without being contact with the sodium hydrogen carbonate solution 57 . That is, the analysis tube 59 is capable of collect a generated gas or the like.
  • the analysis tube 59 is connected to a gas analysis apparatus, not shown, and the collected gas is guided to the analysis apparatus.
  • a copper-containing cluster catalyst 63 (This is for the case of the electrode in Examples. In the case of the electrode in Comparative Examples, it is the copper porous body 63 . The same applies hereinafter.) as a cathode electrode is formed on an ion-exchange membrane 65 .
  • a metal mesh 73 is provided such that the copper-containing cluster catalyst 63 is sandwiched between the metal mesh 73 and the ion-exchange membrane 65 .
  • the metal mesh, the copper-containing cluster catalyst, and the ion-exchange membrane are arranged in turn from the side of the first tank 51 a , and sandwiched between the cathode electrode 69 a and an anode electrode 69 b . Furthermore, the cathode electrode 69 a and the anode electrode 69 b are sandwiched by a sealing member 71 from the outside, and are fixed by a clamp or the like, not shown.
  • the cathode electrode 69 a is a member applying an electric current to the metal mesh 73 , and a ring-shaped Ti/Pt electrode was used.
  • the metal mesh 73 is a copper mesh.
  • the metal mesh 73 electrically contacts with the copper-containing cluster catalyst 63 , and functions as a cathode itself.
  • As the copper mesh “copper 100 mesh metal gauze” (0.11 mm in thickness, manufactured by Nilaco Corporation) was used.
  • the copper-containing cluster catalyst 63 is the above electrode produced in Examples (or Comparative Examples).
  • As the ion-exchange membrane 65 “SELEMION (registered trademark) AMV” manufactured by Asahi Glass Co., Ltd. was used.
  • anode electrode 69 b As the anode electrode 69 b , a ring-shaped Ti/Pt electrode holding a metallic nonwoven fabric 67 as the anode electrode, and electrically contacting with the metallic nonwoven fabric 67 was used. A nonwoven fabric made of Pt was used as the metallic nonwoven fabric 67 . That is, the metallic nonwoven fabric 67 is held in a ring of the ring-shaped anode electrode 69 b.
  • the cathode electrode 69 a and the anode electrode 69 b are connected to the power supply 55 .
  • electrolysis was performed at a current value of 2 mA and a voltage of 2.8 V for 60 minutes with the cathode electrode 69 a as the cathode and the anode electrode 69 b side as the anode.
  • a carbon dioxide gas was bubbled at 10 mL/min from the supply tube 61 into a tank 51 a on the side of the metal mesh 73 and copper-containing cluster catalyst 63 (the opposite side of the ion-exchange membrane 65 ) (arrow F direction in the figure).
  • the gas generated from the cathode was collected with the analysis tube 59 (arrow G direction in the figure), and analyzed by gas chromatography.
  • SUPELCO CARBOXEN 1010PLOT 30 m ⁇ 032 mm ID was used as a column, and FID was used as a detector.
  • the reaction at the anode electrode is as follows.
  • each of the metal-containing cluster catalysts (Examples 1 to 5) has excellent catalytic activity than that of each of the porous body catalysts (Comparative Examples 1 to 4).
  • the amount of the product obtained by the reduction of carbon dioxide in the copper-containing cluster catalyst according to each of Examples 1 to 4 is more than the amount of the product obtained by the porous body catalyst according to each of Comparative Examples 1 to 3 similarly using copper, and the copper-containing cluster catalyst according to each of Examples 1 to 4 has excellent catalytic activity.
  • the amount of the product obtained by the reduction of carbon dioxide in the silver-containing cluster catalyst according to Example 5 is more than the amount of the product obtained by the porous body catalyst according to Comparative Example 4 similarly using silver, and the silver-containing cluster catalyst according to Example 5 has excellent catalytic activity.
  • Example 6 to 27 a carbon material encapsulating a copper-containing cluster, and an electrode including a copper-containing cluster catalyst using the carbon material were produced by a method similar to that of Example 1 except that the number of generations of a phenylazomethine dendrimer, the equivalent amounts of raw materials, the firing condition of a phenylazomethine dendrimer copper cluster, and the like were appropriately changed, and evaluated in a similar manner as with Example 1. The results are shown in Table 2. In Table 2, Examples 1 to 4 are similar to those shown in Table 1.
  • Example 1 As shown in Table 2, it was confirmed that the copper-containing cluster represented by Cu n O m exhibits particularly excellent catalytic activity when a ratio min is 0.67 (Examples 1, 6, 9, 15, and 26). It was confirmed that all the products can be generated in a largest amount when n is particularly 12 (Example 1) in the copper-containing cluster represented by Cu n O m with the ratio min of 0.67, and Example 1 has particularly excellent catalyst efficiency.

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CN113769761A (zh) * 2021-09-22 2021-12-10 电子科技大学 一种硫化镉表面锚定铜原子簇的制备方法及应用
CN116145175A (zh) * 2023-02-22 2023-05-23 兰州大学 电催化剂及其制备方法和应用

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CN110465290B (zh) * 2018-05-11 2022-03-11 天津大学 超薄钯片在促进二氧化碳电还原中的应用
KR20210108387A (ko) 2018-11-28 2021-09-02 오푸스-12 인코포레이티드 전해기 및 사용 방법
EP3899092A1 (en) 2018-12-18 2021-10-27 Opus 12 Incorporated Electrolyzer and method of use
KR102269986B1 (ko) * 2019-11-19 2021-06-30 서울대학교산학협력단 금속 나노 클러스터 촉매 및 그 제조 방법, 금속 나노 클러스터 촉매를 이용한 요소 합성 방법, 및 금속 나노 클러스터 촉매를 포함하는 전기 화학 시스템
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CN113769761A (zh) * 2021-09-22 2021-12-10 电子科技大学 一种硫化镉表面锚定铜原子簇的制备方法及应用
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